Patent GB-562757-A (GB)
Title: Manufacture of new colouring matters
IPC: C09B23/01
Filed: 1942-07-13
Abstract: Dyes of formula <FORM:0562757/IV/1> where R1 and R11 stand for aryl radicals (e.g. o the benzene or naphthalene series) substituted or not and the same or different, and R111 stands for H or for a non-reactive substituent (e.g. an aryl, or alkyl, radical), are prepared by reacting an aldehyde of formula <FORM:0562757/IV/2> with a compound XCH2Y, other than a 2 : 4-diarylpyrrole, containing one or more reactive methylene or methyl groups. Aldehydes specified are 5 - formyl - 2 : 4 - diphenylpyrrole, 5 - formyl - 2 : 4 - di - (sulphophenyl) - pyrrole, 5 - formyl - 2 - phenyl - 4 - (o-chlorophenyl) - pyrrole, and 5 - formyl - 2 - (p - methoxyphenyl) - 4 - phenylpyrrole.  Simple derivatives (e.g. oximes or anils) of the aldehydes may be used.  Reactive methylene or methyl compounds specified are indoxyl, thioindoxyl, 2-alkylindoles, N-methyloxindole, a  : g -diketohydrindene, 4-phenylquinaldine methiodide, 2-quinaldine methiodide, 2-methylbenzoxazole methiodide, 2-methylbenzthiazole methiodide, 1 : 3 : 5-trimethyl-2-methylenedihydroindole, 1 : 2 : 3 : 3 - tetra - methyldihydroindole, 1 - (p - sulphophenyl) - 3 - methyl - 5 - pyrazolone, 1 - phenyl - 3 - methyl - 5 - pyrazolone, cyanacetic ester, chloroacetonitrile, phenylsulphonylacetonitrile, 2 : 4-dinitrotoluene, N-phenylrhodanine, barbituric acids, sulphazones, 2 : 4-dihydroxyquinolines, dihydroresorcinol, benzyl cyanide, cyanoacetophenone, desoxy-benzoin, a -naphthol, 2-keto-2 : 3-dihydrobenzthiazine, and 3 : 31-dinitro-4 : 41-dimethylazobenzene. If compounds containing more than one reactive methylene or methyl group are used, then more than one molecular proportion of the aldehyde will react therewith. The reactants may be heated together in a mutual solvent, e.g. ethanol, in the presence of a base, e.g. piperidine. Water-soluble derivatives are obtained by forming salts with sulphamic acid, by forming quaternary ammonium salts, by sulphonation of the dyes to obtain water-soluble sulphonic acids or salts thereof, or by using reactants containing sulphonic acid groups.  Dyes from sulphonated 5 - formyl - 2 : 4 - diarylpyrroles and pyrazolone derivatives are referred to.  In example 1, N - methyloxindole, 5 - formyl - 2 : 4 - diphenyl - pyrrole, ethanol, and piperidine are boiled together.  The product may be sulphonated by dissolving in concentrated H2SO4 and adding 20 per cent oleum.  In example 2, 2-quinaldine methiodide, 5 - formyl - 2 : 4 - diphenylpyrrole, ethanol, and piperidine are boiled together.  The anhydro base may be formed by addition of caustic soda.  The sulphamate is obtained by addition of sulphamic acid to a solution of the anhydro base in benzene.  In example 3, 1 : 2 : 3 : 3-tetramethyldihydroindoline hydriodide, 5-formyl-2 : 4-diphenylpyrrole, and acetic anhydride are refluxed together. The anhydro base is obtained by adding aqueous NaOH to a solution of the dye in aqueous b -ethoxyethanol.  The sulphamate is obtained by adding sulphamic acid to the benzene solution of the anhydro base. Similar dyes are produced from 5-formyl-2 - phenyl - 4 - (o - chlorophenyl) - pyrrole and 5-formyl - 2 - (p - methoxyphenyl) - 4 - phenylpyrrole.  In example 4, 5-formyl-2-phenyl-4-(o-chlorophenyl) - pyrrole, 4 - phenylquinaldine methiodide, ethanol, and piperidine are refluxed together.  In example 5, 5-formyl-2 : 4-diphenylpyrrole, 2 - methylbenzthiazole ethiodide, ethanol, and piperidine are refluxed together.  Similar dyes are obtained from 5-formyl-2-phenyl-4-(o-chlorophenyl)pyrrole and 5-formyl-2 - (p - methoxyphenyl) - 4 - phenylpyrrole.  In example 6, 2-methylbenzoxazole ethiodide, 5 - formyl - 2 : 4 - diphenylpyrrole, and acetic anhydride are refluxed together. Similar dyes are obtained from 5-formyl-2-phenyl-4-(o-chlorophenyl) - pyrrole and 5 - formyl - 2 - (p - methoxy - phenyl) - 4 - phenylpyrrole.  In example 7, 1-phenyl-3-methyl-5-pyrazolone, 5-formyl-2 : 4-diphenylpyrrole, ethanol, and piperidine are refluxed together.  A similar dye is obtained using 5 - formyl - 2 - phenyl - 4 - (o - chlorophenyl) - pyrrole.  In example 8, 1-p-sulphophenyl-3-methyl - 5 - pyrazolone, 5 - formyl - 2 : 4-diphenylpyrrole, ethanol, and piperidine are refluxed together.  In example 9, N-phenylrhodanine, 5-formyl-2-(p-methoxyphenyl)-4-phenylpyrrole, ethanol, and piperidine are refluxed together.  In example 10, ethyl cyanacetate, 5 - formyl - 2 : 4-diphenylpyrrole, ethanol, and piperidine are refluxed together.  5-Formyl-2 : 4-diphenylpyrrole is prepared by reacting 2 : 4-diphenylpyrrole with formanilide in presence of POC13 below 0 DEG C.  5-Formyl-2-phenyl - 4 - (o - chlorophenyl) - pyrrole, 5 - formyl-2 : 4 - di - (sulphophenyl)-pyrrole and 5-formyl-2 - (p - methoxyphenyl) - 4 - phenylpyrrole are similarly prepared. Specification 562,753 is referred to.  The Provisional Specification also refers to dyes of the general formula in which R111 stands for an alkylamino, benzylideneamino, or acylamino radical.